This invention pertains to certain thermally-stable, anthraquinone colorant compounds (dyes) which contain one or more vinyl groups which render the compounds copolymerizable with reactive vinyl monomers to produce colored, polymeric compositions such as acrylate and methacrylate polymeric materials. The compounds possess good fastness (stability) to ultraviolet (UV) light, good solubility in vinyl monomers, good color strength and excellent thermal stability. The present invention includes acrylic polymeric materials, i.e., polymers derived from acrylic acid esters, methacrylic acid esters and/or other copolymerizable vinyl compounds, having copolymerized therein one or more of the dye compounds of the present invention.
It is known (J.S.D.C., April 1977, pp 114-125) to produce colored polymeric materials by combining a reactive polymer such terepolymers having epoxy groups or polyacryloyl chloride with anthraquinone dyes containing nucleophilic reactive groups such as amino or hydroxy groups; to graft acryloylaminoanthraquinone dyes to the backbone of vinyl or divinyl polymers; and to polymerize anthraquinone dyes containing certain olefinic groups to produce polymeric dyes/pigments. U.S. Pat. No. 4,115,056 describes the preparation of blue, substituted 1,4-diaminoanthraquinone dyes containing one acryloyloxy group and and the use of the dyes in coloring various fibers, especially polyamide fibers. U.S. Pat. No. 4,943,617 discloses liquid crystalline copolymers containing certain blue, substituted 1,5-diamino-4,8-dihydroxyanthraquinone dyes containing an olefinic group copolymerized therein to provide liquid crystal copolymers having high dichromism. U.S. Pat. No. 5,055,602 describes the preparation of certain substituted 1,4-diaminoanthraquinone dyes containing polymerizable acryloyl and methacryloyl groups and their use in coloring polyacrylate contact lens materials by copolymerizing.
U.S. Pat. No. 5,362,812 discloses the conversion of a variety of dye classes, including anthraquinones, into polymeric dyes by (a) polymerizing 2-alkenylazlactones and reacting the polymer with dyes containing nucleophilic groups and by (b) reacting a nucleophilic dye with an alkenylazlactone and then polymerizing the free radically polymerizable dyes thus produced. The polymeric dyes are reported to be useful for photoresist systems and for colorproofing. U.S. Pat. No. 5,367,039 discloses a process for preparing colored vinyl polymers suitable for inks, paints, toners and the like by emulsion polymerization of a vinyl monomer with reactive anthraquinone dyes prepared by functionalizing certain anthraquinone dyes with methacryloyl groups.
The preparation of a variety of dyes, including some anthraquinones, which contain photopolymerizable groups and their use for color filters suitable for use in liquid crystal television sets, color copying machines, photosensitive resist resin compositions, and the like are described in U.S. Pat. No. 5,578,419.
One embodiment of the present invention concerns anthraquinone dye or colorant compounds represented by general Formulae I-XXI set forth below. The dyes having Formulae I-VII are blue-cyan colorants, the dyes having Formulae VIII-XVIII are red-magenta colorants, and the dyes having Formulae XIX-XXI are yellow colorants. 
wherein:
R is selected from hydrogen or 1-3 groups selected from C1-C6-alkyl, C1-C6-alkoxy and halogen;
R1 is selected from C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-cycloalkyl, aryl and xe2x80x94L1xe2x80x94Zxe2x80x94Q; R2=selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-cycloalkyl and aryl;
R3 and R4 are independently selected from C1-C6-alkyl and bromine;
R5 is selected from C1-C6-alkyl, substituted C1-C6 alkyl, C3-C8-cycloalkyl, aryl, heteroaryl, xe2x80x94L1xe2x80x94Zxe2x80x94Q, 
R7 is selected from hydrogen, substituted or unsubstituted C1-C6-alkyl, C1-C6-alkoxy, halogen, hydroxy, substituted or unsubstituted C1-C6-alkylthio, sulfamoyl and substituted sulfamoyl;
R8 is selected from hydrogen and C1-C6-alkyl;
R9 is selected from the groups represented by R1 and xe2x80x94Lxe2x80x94Zxe2x80x94Q;
R10 is selected from hydrogen and halogen;
X is a covalent bond or a divalent linking group selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94CO2xe2x80x94, xe2x80x94CON(Y)xe2x80x94 and xe2x80x94SO2N(Y)xe2x80x94, wherein Y is selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-cycloalkyl, C3-C8-alkenyl, aryl and xe2x80x94Lxe2x80x94Zxe2x80x94Q;
X1 is selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94 and xe2x80x94SO2N(Y)xe2x80x94;
X2 is selected from xe2x80x94CO2xe2x80x94 and xe2x80x94SO2N(Y1), wherein Y1 is a group selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-cycloalkyl, aryl heteroaryl and xe2x80x94CH2-p-C6H4xe2x80x94C(R8)xe2x95x90CH2;
X3 is selected from xe2x80x94CO2xe2x80x94, xe2x80x94SO2N(Y)xe2x80x94;
X4 is selected from xe2x80x94CO2xe2x80x94, xe2x80x94Oxe2x80x94 and xe2x80x94SO2N(Y1)xe2x80x94;
L is a divalent linking group selected from C1-C8-alkylene, C1-C6-alkylene-arylene, arylene, C1-C6-alkylene-arylene -C1-C6-alkylene, C3-C8-cycloalkylene, C1-C6-alkylene-C3-C8-cycloalkylene -C1-C6-alkylene, C1-C6-alkylene-Z1-arylene-Z1-C1-C6-alkylene and C2-C6-alkylene-[xe2x80x94Z1xe2x80x94C2-C6-alkylene-]nxe2x80x94 wherein Z1 is selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 and xe2x80x94SO2xe2x80x94 and n is 1-3;
L1 is a divalent linking group selected from C2-C6-alkylene, C1-C6-alkylene-C3-C8-cycloalkylene-C1-C6-alkylene, C1-C6-alkylene-arylene, C3-C8-cycloalkylene, and C2-C6-alkylene-[xe2x80x94Z1xe2x80x94C2-C6-alkylene-]n-;
L2 is selected from C2-C6-alkylene, C1-C6-alkylene-arylene-C1-C6 alkylene and C1-C6-alkylene-C3-C8-cycloalkylene-C1-C6-alkylene;
Z is a divalent group selected from xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94N(C1-C6-alkyl)xe2x80x94, xe2x80x94N(C3-C8 alkenyl)xe2x80x94, xe2x80x94N(C3-C8 cycloalkyl)xe2x80x94, xe2x80x94N(aryl)xe2x80x94, xe2x80x94N(SO2C1-C6-alkyl) and xe2x80x94N(SO2 aryl)xe2x80x94, provided that when Q is a photopolymerizable optionally substituted maleimide radical, Z represents a covalent bond; Q is an ethylenically-unsaturated, photosensitive polymerizable group; and
m and m1 each is O or 1.
The ethylenically-unsaturated, photosensitive copolymerizable groups represented by Q are selected from the following organic radicals: 
wherein:
R11 is selected from hydrogen and C1-C6-alkyl;
R12 is selected from hydrogen; C1-C6-alkyl; phenyl and phenyl substituted with one or more groups selected from C1-C6-alkyl, C1-C6-alkoxy, xe2x80x94N(C1-C6-alkyl), nitro, cyano, C1-C6-alkoxycarbonyl, C1-C6-alkanoyloxy and halogen; 1- and 2-naphthyl which may be substituted with C1-C6-alkyl or C1-C6-alkoxy; 2- and 3-thienyl which may be substituted with C1-C6-alkyl or halogen; 2- or 3-furyl which may be substituted with C1-C6-alkyl;
R13 and R14 are selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, aryl or may be combined to represent a xe2x80x94[xe2x80x94CH2xe2x80x94]3-5xe2x80x94 radical;
R15 is selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-cycloalkyl and aryl;
R16 is selected from hydrogen, C1-C6-alkyl and aryl.
The term xe2x80x9cC1-C6-alkylxe2x80x9d is used herein to denote a straight or branched chain, saturated, aliphatic hydrocarbon radical containing one to six carbon atoms. The term xe2x80x9csubstituted C1-C6-alkylxe2x80x9d is used to denote a C1-C6-alkyl group substituted with one or more groups, preferably one to three groups, selected from the group consisting of hydroxy, halogen, cyano, aryl, aryloxy, arylthio, C1-C6 alkylthio, C3-C8-cycloalkyl, C1-C6-alkanoyloxy and xe2x80x94[xe2x80x94Oxe2x80x94R17xe2x80x94)xe2x80x94R18, wherein R17 is selected from the group consisting of C1-C6 alkylene, C1-C6-alkylene-arylene, cyclohexylene, arylene, C1-C6-alkylene-cyclohexylene and C1-C6-alkylene-cyclohexylene-C1-C6-alkylene;
R18 is selected from the group consisting of hydrogen, hydroxy, carboxy, C1-C6-alkanoyloxy, C2-C6-alkoxycarbonyl, aryl and C3-C8-cycloalkyl; and p is 1, 2, or 3.
A second embodiment of the present invention pertains to a coating composition comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the dye compounds described above, and (iii) a photoinitiator. A third embodiment of the present invention pertains to a polymeric composition, typically a coating, comprising a polymer of one or more acrylic acid esters, one or more methacrylic acid esters and/or other polymerizable vinyl compounds, having copolymerized therein one or more of the dye compounds described above.
The terms xe2x80x9cC1-C6-alkylenexe2x80x9d and xe2x80x9cC1-C8-alkylenexe2x80x9d are used to denote straight or branched chain, divalent, aliphatic hydrocarbon radicals containing one to six and one to eight carbons, respectively, and these radicals substituted with one to three groups selected from C1-C6-alkoxy, C1-C6-alkoxycarbonyl, C1-C6-alkanoyloxy, hydroxy, aryl and halogen. Similarly, the term xe2x80x9cC2-C6-alkylenexe2x80x9d is used to denote a straight or branched chain, divalent, hydrocarbon radical which may be unsubstituted or substituted as described in this paragraph for the C1-C6-alkylene and C1-C8-alkylene radicals.
The terms xe2x80x9cC1-C6-alkoxyxe2x80x9d, xe2x80x9cC1-C6-alkoxycarbonylxe2x80x9d, xe2x80x9cC1-C6-alkanoyloxyxe2x80x9d and xe2x80x9cC1-C6-alkanoylaminoxe2x80x9d are used to denote radicals corresponding to the structures xe2x80x94OR19, xe2x80x94CO2R19, xe2x80x94OCOR19 and NHCOR19, respectively, wherein R19 is C1-C6-alkyl or substituted C1-C6-alkyl. The term xe2x80x9cC3-C8-alkenylxe2x80x9d is used to denote an aliphatic hydrocarbon radical containing at least one double bond. The term xe2x80x9cC3-C8-cycloalkylxe2x80x9d is used to denote a saturated, carbocyclic hydrocarbon radical having three to eight carbon which may be unsubstituted or substituted with one to three C1-C6-alkyl group(s). The term xe2x80x9cC3-C8-cycloalkylenlexe2x80x9d is used to denote a carbocyclic, divalent hydrocarbon radical which contains three to eight carbon atoms, preferably five or six carbons.
The term xe2x80x9carylxe2x80x9d as used herein denotes phenyl and phenyl substituted with one to three substituents selected from C1-C6-alkyl, substituted C1-C6-alkyl, C1-C6-alkoxy, halogen, carboxy, cyano, C1-C6-alkanoyloxy, C1-C6-alkylthio, C1-C6-alkylsulfonyl, trifluoromethyl, hydroxy, C1-C6-alkoxycarbonyl, C1-C6-alkanoylamino and xe2x80x94Oxe2x80x94R20, Sxe2x80x94R20, xe2x80x94SO2xe2x80x94R20, xe2x80x94NHSO2R20 and xe2x80x94NHCO2R20, wherein R20 is phenyl or phenyl substituted with one to three groups selected from C1-C6-alkyl, C1-C6-alkoxy and halogen. The term xe2x80x9carylenexe2x80x9d as used herein denotes includes 1,2-, 1,3- and 1,4-phenylene and such divalent radicals substituted with one to three groups selected from C1-C6-alkyl, C1-C6-alkoxy and halogen. The term xe2x80x9cheteroarylxe2x80x9d as used herein denotes a 5- or 6-membered aromatic ring containing one to three hetero atom selected from oxygen, sulfur and nitrogen. Examples of such heteroaryl groups are thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, pyridyl, pyrimidyl, benzoxazolyl, benothiazolyl, benzimidazolyl, indolyl and the like. The heteroaryl radicals may be substituted with one to three groups selected from C1-C6-alkyl, C1-C6-alkoxy, substituted C1-C6-alkyl, halogen, C1-C6-alkylthio, aryl, arylthio, aryloxy, C1-C6-alkoxycarbonyl and C1-C6-alkanoylamino.
The term xe2x80x9chalogenxe2x80x9d is used to include fluorine, chlorine, bromine, and iodine. The terms xe2x80x9csulfamoyl and substituted sulfamoylxe2x80x9d denote radicals having the structure xe2x80x94SO2N(R21)R22, wherein R21 and R22 are independently selected from hydrogen, C1-C6-alkyl, substituted C1-C6-alkyl, C3-C8-alkenyl, C3-C8-cycloalkyl, aryl and heteroaryl.
The preferred dye compounds of Formulae I, II, III, IV, V, VI, VIII, IX, X, XII, XIII, XIV, XVI, XVII, XIX, and XX are those where Z is xe2x80x94Oxe2x80x94. These dyes are prepared by reacting the corresponding dihydroxy dye [Dye (OH)2] with a reagent to introduce the reactive vinyl functionality. For example, the dyes wherein Q corresponds to structure Ia, VIa, XIa, respectively, are prepared by reacting the dihydroxy dyes with the corresponding acid chlorides and/or anhydrides as follows: 
The dyes wherein Z is xe2x80x94Oxe2x80x94 and Q corresponds to structures IIa, IIIa, and VIIIa are prepared by reacting the dihydroxy dyes with the corresponding isocyanates: 
The dyes were Z is xe2x80x94Oxe2x80x94 and where Q corresponds to structure IVa are prepared by reacting the dihydroxy dyes with 2-alkenylazlactones as generally described in Encyclopedia of Polymer Science and Eng., Second Ed., Vol. 11, John Wiley and Sons, pp. 558-571: 
The dyes wherein Z is xe2x80x94Oxe2x80x94 and Q corresponds to structure Va are generally prepared by reacting the dihydroxy dyes with maleic anhydride to give the mono maleate esters: 
The remaining acid groups may be esterified by the usual type esterification reactions such as heating in alcohols in the presence of acid catalysts and reacting the alkali metal salts of the acids with alkylating agents such as alkyl halides, alkyl sulfates and alkyl sulfonates, such as methyl 4-toluene sulfonate, to prepare the methyl ester. Fumaric acid and its derivatives also may be used to prepare the dyes where Q is radical Va. Itaconic anhydride (methylenesuccinic anhydride) may be used to react with the dihydroxy dyes to prepare the functionalized dyes wherein Z is xe2x80x94Oxe2x80x94 and Q corresponds to structure XIIa (R15xe2x95x90H). These acidic compounds may be esterified as described above for preparing the dyes where Q corresponds to structure Va.
Anthraquinone dyes containing aliphatic hydroxy groups useful for reacting as described above to produce dyes containing reactive Q groups are disclosed in U.S. Pat. Nos. 4,267,306, 4,359,570, 4,403,092, 4,804,719, 4,999,418, 5,032,670, 5,194,463, 5,372,864, 5,955,564 and 5,962,557. Anthraquinone dyes containing 1(H)-1,2,4-triazol-3-ylthio groups which are useful in preparing dyes of Formulae III, IX, XIII and XX are disclosed in U.S. Pat. Nos. 3,689,501, 4,267,306, 5,962,557 and U.S. Pat. No. 6,197,223. Anthraquinone dyes containing carboxy groups and which are useful in the practice of the invention are disclosed in U.S. Pat. Nos. 4,359,570, 4,403,092, 4,999,418, 5,372,864, 5,955,564, 5,962,557 and 6,197,223. Hydroxy alkyl groups may be introduced into these compounds by alkylation of the acids with hydroxyalkyl halides or alkylene carbonates to give the hydroxyalkyl derivatives useful for reacting further as shown herein to introduce reactive Q groups.
To prepare the dyes wherein Z is xe2x80x94Sxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94N(C1-C6 alkyl)xe2x80x94, xe2x80x94N(C3-C8 alkenyl)xe2x80x94, xe2x80x94N(C3-C8 cycloalkyl)xe2x80x94, xe2x80x94N(aryl)xe2x80x94, xe2x80x94N(SO2 C1-C6 alkyl)xe2x80x94 and xe2x80x94N(SO2 aryl)xe2x80x94, the corresponding anthraquinone dyes containing two of the following nucleophilic ZH groups, respectively, are reacted with the reagents mentioned above for preparing the dyes where Zxe2x95x90xe2x80x94Oxe2x80x94: xe2x80x94SH, xe2x80x94NH(C1-C6 alkyl), xe2x80x94NH(C3-C8 alkenyl), xe2x80x94NH(C3-C8 cycloalkyl), xe2x80x94NH(aryl)xe2x80x94, NH(SO2 C1-C6 alkyl) and xe2x80x94NH(SO2 aryl). All of the dyes mentioned above containing two ZH groups may be reacted with vinylsulfonyl halides to prepare dyes where Qxe2x95x90xe2x80x94SO2C(R11)xe2x95x90CH2 (Structure IXa). When Q corresponds to Structure IXa, the preferred Z group is xe2x80x94NHxe2x80x94. Dyes wherein Q corresponds to structure Xa and XIIIa and Z is a covalent bond are prepared by reacting dyes containing two primary amine groups with, for example, maleic anhydride and itaconic anhydride, respectively.
The functionalized dyes of Formulae VII, XI, XV, XVIII and XXI wherein X2 and X4 are xe2x80x94CO2xe2x80x94 are prepared by alkylating the intermediate dye containing two carboxy groups with an alkylating agent having the structure ClCH2-p-C6H4xe2x80x94C(R8)xe2x95x90CH2, with 4-vinylbenzyl chloride (R8xe2x95x90H) being particularly preferred. The reaction is easily accomplished in the presence of alkali metal carbonates and trialkyl amines as bases. The functionalized dyes corresponding to Formulae III, IX, XIII and XX wherein m is O are prepared by reacting the intermediate dyes containing two 1(H)-1,2,4-triazol-3-ylthio groups with an alkylating agent having the structure ClCH2-p-C6H4xe2x80x94C(R8)xe2x95x90CH2, with 4-vinylbenzyl chloride (R8xe2x95x90H) being preferred, in the presence of a base such as alkali metal carbonates or trialkylamines.
A group of preferred anthraquinone compounds comprise compounds having structures XVI and XIX wherein X3 is xe2x80x94CO2xe2x80x94, L is propylene, 1,4-cyclohexylenedimethylene or 2,2-dimethyltrimethylene, R is hydrogen, Z is xe2x80x94Oxe2x80x94, and Q is an organic radical having the structure xe2x80x94COC(R11)xe2x95x90CH2 wherein R11 is hydrogen, methyl or ethyl, or Q is an organic radical having structure VIIIa wherein R11, R13 and R14 each is methyl.
The yellow, red-magenta, blue-cyan dyes of this invention are particularly useful for making combination shades as subtractive colors. They have particular value for copolymerizing into acrylic polymeric materials by free radical polymerization, having one or more advantages over the prior art dyes such as thermal stability, solubility in the acrylate or methacrylate ester comonomer(s) to be used, fastness to UV light, color strength, ease of manufacture and the like. The dyes of this invention are particularly useful for providing acrylic polymer color coatings for glass optical fibers where good thermal stability of dyes is required.
The copolymerizable dye compounds provided by the present invention and the preparation thereof are further illustrated by the following examples.